Li2O-SiO2 glasses with Li2O content up to 35 mol% in nanoscale dimensions have been synthesized within the pores of a pellet formed by CuO nanoparticles of diameter 17 nm. The resistivities of the nanoglasses produced are almost four orders of magnitude lower than that of the bulk glass of similar composition. The activation energy of conduction is also smaller than the bulk counterpart. This is due to an increase in free volume of the nanoglass because it cannot relax into its metastable configuration as a result of nanosize effect. The high frequency exponent of the frequency dependent electrical conductivity has a value characterizing one-dimensional ionic transport. (C) 2011 Elsevier B.V. All rights reserved.